{
  "abstract": "The unique physicochemical properties of chalcogenides containing post-transition metals are often governed by the stereochemical activity of their ns² lone pairs. A comparative structural analysis of bournonite (CuPbSbS₃) and aikinite (CuPbBiS₃) reveals that CuPbSbS₃ has a larger unit cell volume (V = 552.58 ų) than CuPbBiS₃ (V = 534.42 ų), despite antimony (Sb³⁺) being smaller than bismuth (Bi³⁺). This counterintuitive trend originates from the stronger lone pair effect of Sb³⁺, which induces a larger static distortion, leading to a tetrahedral SbS3L (L-lone pair) coordination, while Bi³⁺ exhibits a less asymmetric distortion corresponding to the more compact square-pyramidal BiS5 (or octahedral BiS5L) coordination. These structural differences are corroborated by temperature-dependent Raman spectroscopy, which captures distinct vibrational behaviors reflective of differing lattice dynamics. CuPbSbS₃ exhibits higher anharmonicity, as quantified by anharmonicity coefficients extracted from Raman data. Electron localization function analysis and crystal orbital Hamilton population further confirm the higher activity of the Sb³⁺ lone pair compared to Bi³⁺. Interestingly, despite the lower atomic mass of Sb relative to Bi, both compounds exhibit nearly identical acoustic-phonon cutoff frequencies. Consequently, both CuPbSbS₃ and CuPbBiS₃ display partially suppressed Umklapp scattering and comparable low lattice thermal conductivities at high temperatures, despite their compositional and structural differences.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 17,
  "authors": [
    {
      "name": "Minati Tiadi"
    },
    {
      "name": "Animesh Bhui"
    },
    {
      "name": "Mohammad Ubaid"
    },
    {
      "name": "Pierric Lemoine"
    },
    {
      "name": "Carmelo Prestipino"
    },
    {
      "name": "Bernard Raveau"
    },
    {
      "name": "Gaelle Riou"
    },
    {
      "name": "Lei Wu"
    },
    {
      "name": "Bin Zhang"
    },
    {
      "name": "Xiaoyuan Zhou"
    },
    {
      "name": "Christophe Candolfi"
    },
    {
      "name": "Priyanshu Sharma"
    },
    {
      "name": "Koushik Pal"
    },
    {
      "name": "Prithwija Mandal"
    },
    {
      "name": "Ajay Soni"
    },
    {
      "name": "Adèle Renaud"
    },
    {
      "name": "Emmanuel Guilmeau"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/9whw61455m4ea.bib",
  "cited_by": 3,
  "doi": "10.1021/acs.chemmater.6c00417",
  "fulltext_url": null,
  "id": "9whw61455m4ea",
  "issns": [
    "0897-4756",
    "1520-5002"
  ],
  "landing_url": "https://hal.science/hal-05605735v1",
  "language": "en",
  "licence": "CC-BY-NC-4.0",
  "licence_label": "CC BY-NC 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "hal",
      "0.chim"
    ],
    [
      "hal",
      "1.chim.inor"
    ],
    [
      "hal",
      "1.chim.mate"
    ],
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      "hal",
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    ],
    [
      "openalex",
      "2504|Crystal Structures and Properties"
    ]
  ],
  "openalex": "W7154579749",
  "pdf_url": "https://hal.science/hal-05605735/document",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-17",
  "publisher": "American Chemical Society",
  "ris": "https://research.draconitic.com/paper/9whw61455m4ea.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:35Z",
      "native_id": "hal-05605735",
      "source": "hal",
      "url": "https://hal.science/hal-05605735v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "hal:1.chim.inor",
      "subfield": "inorganic"
    },
    {
      "field": "chemistry",
      "origin": "hal:1.chim.mate",
      "subfield": "materials-polymers"
    },
    {
      "field": "chemistry",
      "origin": "hal:1.chim.theo",
      "subfield": "theoretical"
    }
  ],
  "title": "Contrasting Lone-Pair Stereochemistry in Sb³⁺ and Bi³⁺ Chalcogenides: Implications for Structure and Phonon Transport",
  "title_text": "Contrasting Lone-Pair Stereochemistry in Sb³⁺ and Bi³⁺ Chalcogenides: Implications for Structure and Phonon Transport",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:17:35Z",
  "url": "https://research.draconitic.com/paper/9whw61455m4ea",
  "venue": "Chemistry of Materials",
  "versions": []
}